Tin tetrachloride → (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene

HRID 422155노트

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HRID 422155 반응식
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([S:9][CH2:10][C@@H:11]2[C@:20]3([CH3:21])[C@H:15]([C:16]([CH3:23])([CH3:22])[CH2:17][CH2:18][CH2:19]3)[CH2:14][CH2:13][C@@:12]2([CH3:25])O)[CH:6]=[CH:7][CH:8]=1.Cl[Sn](Cl)(Cl)Cl>C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:6]([C@@:12]3([CH3:25])[C@H:11]([CH2:10][S:9]2)[C@:20]2([CH3:21])[C@H:15]([C:16]([CH3:23])([CH3:22])[CH2:17][CH2:18][CH2:19]2)[CH2:14][CH2:13]3)=[CH:7][CH:8]=1

참가 물질

4

반응물 2

HCID 24287Tin tetrachlorideHCID 58294805(1R,2R,4aS,8aS)-1-{[(3-methoxyphenyl)sulfanyl]methyl}-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol

생성물 1

HCID 53240551(1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene수율 46.3%

시약·촉매·용매 1

HCID 6344Dichloromethane용매2회

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온도
-78 °C

실험 절차

To a solution of (1R,2R,4aS,8aS)-1-{[(3-methoxyphenyl)sulfanyl]methyl}-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol (12b) (2.5 g, 6.9 mmol) in CH2Cl2 (70 mL), cooled to −78° C., a solution of SnCl4 (3.22 mL, 27.6 mmol) in CH2Cl2 (30 mL) was added dropwise. The mixture was stirred at −78° C. for 4 h. The reaction was quenched with water (100 mL), and the organic layer was separated, dried (Na2SO4), and concentrated. Purification by column chromatography on silica gel (Hexanes/toluene, 2:1) gave (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 51) (1.10 g, 46%) as a white solid. 1H NMR (CDCl3): δ 7.19 (d, 1H), 6.58 (m, 2H), 3.72 (s, 3H), 2.95 (q, 2H), 2.40 (m, 1H), 1.84-1.35 (m, 9H), 1.20 (s, 3H), 1.18-0.99 (m, 2H), 0.95 (s, 3H), 0.85 (s, 3H), 0.82 (s, 3H). (1R,10R,11S,16S)-3-Methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 52) (0.44 g, 19%) was also isolated as a white solid. 1H NMR (CDCl3): δ 6.96 (t, 1H), 6.67 (d, 1H), 6.56 (d, 1H), 3.78 (s, 3H), 3.32 (m, 1H), 2.82 (q, 2H), 1.82-1.40 (m, 7H), 1.38 (s, 3H), 1.35-0.98 (m, 3H), 0.92 (s, 3H), 0.95 (m, 1H), 0.87 (s, 3H), 0.83 (s, 3H).

후처리

  1. customThe reaction was quenched with water (100 mL)
  2. customthe organic layer was separated
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated
  5. customPurification by column chromatography on silica gel (Hexanes/toluene, 2:1)

출처 및 근거

ORD 기록
ord-11288067561d4f0aa5dc5748234ae8de
출처 데이터셋
uspto-grants-2012_01
특허 번호
US08101605B2

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